Process and system for capture of carbon dioxide

ABSTRACT

A process for absorbing carbon dioxide from a gas stream containing carbon dioxide, including contacting the gas stream with an aqueous composition having a substituted heteroaromatic compound including a six-membered heteroaromatic ring comprising from 1 to 3 nitrogen atoms in the heteroaromatic ring and at least one substituent wherein at least one of the substituents is of formula —R1NH2 wherein R1 is selected from C1 to C6 alkylene and ethers of formula —R2—O—R3— wherein R2 and R3 are C1 to C3 alkylene.

RELATED APPLICATION

This application is an application under 35 U.S.C. 371 of International Application No. PCT/AU2018/050488 filed on 22 May 2018, which claims the benefit of Australian Application No.: 2017901937 filed 22 May 2017, the entire contents of which are incorporated herein by reference.

FIELD

The invention relates to a process and system for capture of carbon dioxide from gas streams.

BACKGROUND

Emission of carbon dioxide is considered the main cause of the greenhouse effect and global warming. In the Kyoto Protocol the United Nations Framework Convention on Climate Change has set targets for the reduction of greenhouse gas emissions.

One method of reducing atmospheric CO₂ emissions is through its capture and subsequent geological storage. In post combustion capture, the CO₂ in flue gas is first separated from nitrogen and residual oxygen using a suitable solvent in an absorber. The CO₂ is then removed from the solvent in a process called stripping (or regeneration), thus allowing the solvent to be reused. The stripped CO₂ is then liquefied by compression and cooling, with appropriate drying steps to prevent hydrate formation. Post combustion capture in this form is applicable to a variety of CO₂ sources including power stations, steel plants, cement kilns, calciners, biogas plants, natural gas processing, methane reforming and smelters.

Aqueous amine solutions and alkanolamine solutions in particular, have been investigated as solvents in post combustion CO₂ capture. The capture process involves a series of chemical reactions that take place between water, the amine and carbon dioxide. Amines are weak bases, and may undergo acid-base reactions. Once dissolved into the amine solution, the aqueous CO₂ reacts with water and the neutral form of the amine react to generate carbamate, protonated amine, carbonic acid (H₂CO₃), aqueous bicarbonate (HCO₃ ⁻) ions and aqueous carbonate (CO₃ ²⁻) ions.

CO₂ desorption is achieved by heating of an aqueous amine solution containing CO₂. The two major effects of heating are to reduce the physical solubility of CO₂ in the solution, and to reduce the pKa of the amine resulting in a concomitant reduction in pH and in CO₂ absorption capacity, the net effect of which is CO₂ release. The extent of the reduction in pKa is governed by the enthalpy of the amine protonation reaction which in turn is governed by the amine chemical structure. All the other reactions, including carbamate formation, have small reaction enthalpies and are insensitive to temperature. Typically, the enthalpy of amine protonation is four to eight times larger than the enthalpies of the carbonate reactions and two to four times larger than the enthalpy of carbamate formation. It is the lowering of the pH upon heating that drives the reversal of carbamate and carbonate/bicarbonate formation during desorption, rather than any significant reduction in stability.

The cyclic capacity (α_(cyclic)) of an aqueous amine solution is defined as the moles of CO₂ that can be absorbed and released per mole of amine by cycling the absorbent between low temperature (α_(rich)) and high temperature (α_(lean)): α_(cyclic)=α_(rich)−α_(lean). In terms of chemistry, this cyclic capacity is primarily governed by the change in amine pKa with temperature. The larger this cyclic capacity, the more efficient the amine. 30 wt % monoethanolamine, which is currently employed in industrial CO₂ capture, possesses an undesirable cyclic capacity of approximately α_(cyclic)=0.11 (40° C.-80° C.).

US Publication 2015/0367281 describes a process for absorption of an acid gas which involves contacting the acid gas with a benzylamine compound and a cosolvent which reduces the vapour pressure of the benzylamine. The use of certain cosolvents also ameliorates the problem precipitate formation due to low solubility of the anion formed from reaction of the benzylamine compound with carbon dioxide.

There remains a need to identify amines and systems which provide improved properties and/or reduce problems in carbon dioxide capture and release.

SUMMARY OF INVENTION

The invention provides a process for absorbing carbon dioxide from a gas stream containing carbon dioxide, comprising contacting the gas stream with an aqueous absorbent composition comprising a substituted heteroaromatic compound comprising an six-membered heteroaromatic ring comprising from 1 to 3 nitrogen atoms in the heteroaromatic ring and at least one substituent wherein at least one substituent is of formula —R¹NH₂ wherein R¹ is selected from the group consisting of C₁ to C₆ alkylene and ethers of formula —R²—O—R³— wherein R² and R³ are C₁ to C₃ alkylene.

In one embodiment there is further provided a composition of adsorbed carbon dioxide comprising:

-   -   A. an aqueous solvent;     -   B. at least one absorbent compound for carbon dioxide comprising         a substituted heteroaromatic compound comprising a six membered         heteroaromatic ring comprising from 1 to 3 nitrogen atoms in the         heteroaromatic ring and at least one substituent, wherein at         least one of the substituents is, of formula —R¹NH₂ wherein R¹         is selected from the group consisting of C₁ to C₆ alkylene and         ethers of formula —R²—O—R³— wherein R² and R³ are C₁ to C₃         alkylene; and     -   C. absorbed carbon dioxide, wherein the absorbed carbon dioxide         is at a concentration above the equilibrium concentration when         the solution is exposed to air at below the boiling point of the         solvent.

In yet a further embodiment there is provided a use of an aqueous solution of a substituted heteroaromatic compound in capture of carbon dioxide in a gas stream comprising carbon dioxide, wherein the substituted heteroaromatic compound comprises a heteroaromatic six-membered ring comprising from 1 to 3 nitrogen atoms in the heteroaromatic ring and at least one substituent wherein at least of the substituents is of formula —R¹NH₂ wherein R¹ is selected from the group consisting of C₁ to C₆ alkylene, C₁ to C₆ oxy-alkylene and ethers of formula —R²—O—R³— wherein R² and R³ are C₁ to C₃ alkylene.

In one set of embodiments the concentration of substituted heteroaromatic compound is 1 wt % to 80 wt % of the aqueous composition, preferably 10 wt % to 80 wt % of the aqueous composition.

In one set of embodiments the amount of water in the aqueous composition at least 10 wt %, preferably at least 20 wt %.

The process of the invention may also be carried out using a further absorbent for carbon dioxide in addition to the substituted heteroaromatic compound. The weight ratio of the substituted heteroaromatic compound to further absorbent may, for example, be from 1:10 to 10:1.

The substituted heteroaromatic compound of the composition provides a high cyclic capacity for carbon dioxide allowing efficient capture and desorption of carbon dioxide while also providing a low vapour pressure in aqueous solution and good solubility of the substituted heteroaromatic compound and species formed on absorption of carbon dioxide. The aqueous composition may therefore be used without a requirement for specific co-solvents and provides flexibiity in formulating aqueous compositions for carbon dioxide capture and release.

We have found that the long term stability of the substituted heteroaromatic compound during CO₂ capture, particularly where R¹ is methylene, is enhanced in the presence of a further amine of higher basicity than the substituted heteroaromatic compound. In a preferred embodiment the absorbent further comprises an amine selected from tertiary amines and primary and secondary sterically hindered amines and mixtures thereof having a higher basicity than the substituted heteroaromatic compound. In particular, in the case where R¹ is methylene such as for (aminomethyl)pyridines the further amine selected from tertiary amines and primary and secondary sterically hindered amines and mixtures thereof typically has a pKa of at least 8.85 at 25° C. A pKa of 8.85 is about 0.25 above the pKa of (aminomethyl)pyridines specifically each of 2-(aminomethyl)pyridine, 3-(aminomethyl)pyridine and 4-(aminomethyl)pyridine.

As used herein, except where the context requires otherwise, the term “comprise” and variations of the term, such as “comprising”, “comprises” and “comprised”, are not intended to exclude further additives, components, integers or steps.

DETAILED DESCRIPTION Brief Description of Drawings

Examples of the invention are described with reference to the attached drawings.

In the drawings:

FIG. 1 is a schematic diagram of a system used for removing carbon dioxide from a gas mixture according to the present invention.

FIG. 2 show part sectioned views of Wetted Wall Column (WWC) apparatus and the column portion of the WWC apparatus used in evaluating and comparing CO₂ absorption rates.

FIG. 3 is a graph including 5 plots showing the overall CO₂ mass transfer coefficients, K_(G), at 40.0° C. for a series of aqueous (aminomethyl)pyridine (AMPy) absorbents and aqueous monoethanolamine (MEA) from 0.0-0.4 CO₂/mole amine. The (aminomethyl)pyridines examined include 2-(aminomethyl)pyridine (2-AMPy), 3-(aminomethyl)pyridine (3-AMPy) and 4-(aminomethyl)pyridine (4-AMPy) each at a concentration of 6.0M. Monoethanolamine (MEA) is included for comparison. The plots, at left hand side of the graph are in the order of, from to bottom, 2-AMPy, 3-AMPy, 4-AMPy, MEA.

FIG. 4 is a graph of vapour liquid equilibria data comparing the amount of CO₂ absorbed as a function of CO₂ partial pressure for 6.0M 3-AMPy and 2.6M BZA each at 295K and 313K and 333K. The additional capacity of the more concentrated 3-AMPy absorbent is apparent.

FIG. 5 is a graph having 5 plots showing the overall CO₂ mass transfer coefficients (K_(G)) at 40° C. for a series of 4-AMPy absorbents and blends of from 0.0 to 0.4 moles CO₂/moles amine. The plots include, from top to bottom at the left hand side of the graph: 3M 4-AMPy+3.0M MEA, 6.0M 4-AMPy, 6.0M MEA, 3.0M 4-AMPy+3.0M DMEA and 3.0M 4-AMPy+3.0M AMP.

FIG. 6 is a graph including 4 plots viscosity of absorbent solutions at 40° C. against CO₂ loadings from 0.0-0.4 moles CO2/total moles amine for aqueous absorbent solution including absorbent solutions of, from top to bottom at the left hand side of the graph: 3.0M 4-AMPy+3.0M AMP; 3.0M 4-AMP+3.0M DMEA; 6M 4-AMPy; and 3.0M 4-AMPy+3.0M MEA.

FIG. 7 is a graph having 5 plots comparing the model estimated reboiler duty (kJ/kg CO₂) for a range of absorbents as a function of the ratio of liquid and gas flow rates (L/G) (kg/kg) for absorbents from top to bottom at right hand side of the graph of 30 wt % MEA; 4:2 3-AMPy:AMP; 5:1M 3-AMPy:AMP; 6M 3-AMPy; 3:3M3-AMPy:AMP.

FIG. 8 is a graph comparing the reboiler energy requirement (GJ/tonne CO₂) with increasing liquid/gas flow ratio (kg/kg) for 90% capture at 101.3 kPa (15 kPa CO₂) for aqueous 6M 3-AMPy against 5M (30 wt %) MEA.

FIG. 9 is a graph showing the 3-AMPy and imine dimer concentration by IR spectroscopy (solid points) and HPLC (circles) over 1500 hours of operation.

FIG. 10 is a graph showing the change in concentration with time of operation of the pilot plant of 3-AMPy, AMP and imine dimer formed from 3-AMPy using the aqueous absorbent solution containing 3M 3-AMPy and 3M AMP in capture of CO₂.

FIG. 11 is a graph which compares the enthalpy and entropy of protonation of a range of amines. The red squares allow comparison of 4 different aminomethyl aromatic compounds and 2-phenyethylamine to illustrate the difference between a methyl linking group and a linking group of an alkyl chain specifically ethyl.

The aqueous absorbent composition for absorption of carbon dioxide from the gas stream comprises an optionally substituted six-membered heteroaromatic ring comprising from 1 to 3 nitrogen atoms in the heteroaromatic ring and at least one substituent wherein at least one substituent is of formula —R¹NH₂ wherein R¹ is selected from the group consisting of C₁ to C₆ alkylene and ethers of formula —R²—O—R³— wherein R² and R³ are C₁ to C₃ alkylene.

In one set of embodiments the optionally substituted six membered heteroaromatic ring is of formula (I):

wherein

X is independently selected from N and the group CR where at least three of X are CR;

R are independently selected from the group consisting of hydrogen, C₁ to C₄ alkyl, hydroxy, hydroxy-C₁ to C₄ alkyl, C₁ to C₄ alkoxy, C₁ to C₄ alkoxy-(C₁ to C₄ alkyl) and at least one R is the group of formula —R¹—NH₂ wherein R¹ is selected from the group consisting of C₁ to C₆ alkylene, C₁ to C₆ oxyalkylene and ethers of formula —R²—O—R³— where R² and R³ are C₁ to Ca alkylene. R¹ is most preferably methylene.

Preferred compounds of formula I are selected from formula Ia, Ib, Ic, Id and mixtures of two or more thereof:

wherein

R¹ is a carbon substituent and is selected from the group consisting of C₁ to C₆ alkylene and ethers of formula —R²—O—R³ wherein R² and R³ are C₁ to C₃ alkylene and R¹ is most preferably methylene;

R⁴ is an optional carbon substituent selected from the group consisting of C₁ to C₄ alkyl, hydroxy, hydroxy —C₁ to C₄ alkyl, C₁ to C₄ alkoxy. C₁ to C₄ alkoxy-(C₁ to C₄ alkyl); and

n is 0, 1 or 2.

Preferably formula I is of formula Ia:

wherein

R¹ is a carbon substituent and is selected from the group consisting of C₁ to C₆ alkylene and ethers of formula —R²—O—R³ wherein R² and R³ are C₁ to C₃ alkylene and R¹ is preferably methylene;

R⁴ is an optional carbon substituent selected from the group consisting of C₁ to C₄ alkyl, hydroxy, hydroxy —C₁ to C₄ alkyl, —C₁ to C₄ alkoxy, C₁ to C₄ alkoxy-(C₁ to C₄ alkyl); and

n is 0, 1 or 2.

Still more preferably the substituted heteroaromatic compound is selected from the group consisting of formula IIa, IIb, IIc and mixtures of two or more thereof:

wherein R¹ is selected from the group consisting of C₁ to C₄ alkylene, preferably methylene.

The substituted heteroaromatic compound includes a substituent group R¹ which is a group that links the amino group (NH₂) to the heteroaromatic ring. Specific examples of the substituent R¹ may be selected from the group consisting of:

—CH₂—, —CH₂CH—, —CH₂CH₂(CH₃)—, —CH₂(CH₃)CH₂—

—CH₂(CH₂—CH₃)—; and

—CH₂CH₂—OCH₂CH₂—.

Examples of optionally substituted heteroaromatic compounds are selected from the group consisting of 2-[amino(C₁ to C₄ alkyl)]pyridine, 3-[amino(C₁ to C₄ alkyl)]pyridine and 4-[amino(C₁ to C₄ alkyl)]pyridine.

Examples of substituted heteroaromatic compounds include aminomethylpyridines including 2-(aminomethyl)pyridine, 3-(aminomethyl)pyridine and 4-(aminomethyl)pyridine 3-aminoethyl pyridine, 3-(amino-2-methylethyl)pyridine, 3-(1-aminopropyl)pyridine, 3-(2-aminopropyl)pyridine or mixture of two or more thereof. Most preferably the substituted heteroaromatic compound is selected from the group of 2-(aminomethyl)pyridine, 3-(aminomethyl)pyridine, 4-(aminomethyl)pyridine and mixture of two or more thereof.

The absorbent composition need not include ionic liquids or organic salts such as imidazolium cation or quaternary ammonium salts and will typically include a water content of more than 15 wt % of the absorbent composition such as at least 20 wt %.

Compositions of the substituted heteroaromatic compound, particularly the (aminomethyl)pyridines, have lower susceptibility to thermal and oxidative degradation than a 30 wt % MEA solution due to the inherent chemical stability imparted by the heteroaromatic ring structure. Preferably the cyclic absorption capacity of the solution for CO₂ is comparable to that of a tertiary or sterically hindered amine solution and the rate of absorption of the target gas is comparable to or better than a 30 wt % MEA solution.

At least one of the substituted heteroaromatic compounds may constitute the total of the carbon dioxide absorbent compound or may be present in solution with other suitable carbon dioxide absorbent compounds so that the total gas absorbent compounds comprise one or more gas absorbent compounds in addition to the substituted heteroaromatic compound. The substituted heteroaromatic compound preferably comprises at least 1 wt %, more preferably 1 wt % to 80 wt %, still more preferably 1.5 wt % to 80 wt %, even more preferably 5 wt % to 80 wt %, more preferably 10 wt % to 80 wt %, such as 15 wt % to 80 wt %, 20 wt % to 80 wt % or 25 wt % to 80 wt % relative to the total weight of the solution. In some embodiments the concentration of the substituted heteroaromatic compound in the aqueous composition is from 30 wt % to 80 wt % such as 40 wt % to 80 wt %, 50 Wt % to 80 wt % or 60 wt % to 80 wt %. The high solubility of the substituted heteroaromatic compound allows high loadings to be used in aqueous solution and also provides a solution stable intermediate in the carbon dioxide absorption process. It therefore provides significant practical advantages in this respect when compared with benzyl amine and its derivatives.

The total wt % of the at least one absorbent compound (including the substituted heteroaromatic compound) in solution is preferably at least 20 wt %, more preferably at least 25 wt %, still more preferably at least 30 wt %, even more preferably at least 40 wt % and yet even more preferably at least 50 wt % relative to the total weight of the solution. This component will typically consists of the substituted heteroaromatic compound and optionally one or more compounds selected from amines and in the preferred embodiment at least one of the aminomethyl substituted heteroaromatic compounds and one or more amines selected from tertiary amine or sterically hindered primary or secondary amine which has a higher basicity than the substituted heteroaromatic compounds.

In one set of embodiments the absorbent composition may comprise:

the heteroaromatic compound in an amount of 10 wt % to 80 wt % such as 15 wt % to 80 wt %, 20 wt % to 80 wt % or 25 wt % to 80 wt % relative to the total weight of the solution;

optionally a further amine absorbent for carbon dioxide in an amount of up to 70 wt % such as from 10 wt % to 70 wt %;

water in an amount of at least 10 wt % such as from 10 wt % to 90 wt % or 20 wt % to 80 wt %.

Further components may be present such as solvents solutes or other materials.

When the additional amine absorbent for carbon dioxide is present the weight ratio of the substituted heteroaromatic to further amine may, for example, be in the range of from 99:1 to 1:10 such as 1:10 to 10:1 or 1:5 to 5:1.

In one embodiment the solution contacted with the gas stream comprises one or more additional carbon dioxide gas absorbing compounds selected from amines and imidazoles in addition to the substituted heteroaromatic compound. The one or more additional amines may be selected from primary, secondary and tertiary amines.

Examples of suitable amines include primary amines such as monoethanolamine, ethylenediamine, 2-amino-2-methyl-1-propanol. 2-amino-2-methyl-ethanolamine and benzylamine; secondary amines such as N-methylethanolamine, piperazine, piperidine and substituted piperidine, 3-piperidinemethanol, 3-piperidineethanol, 2-piperidinemethanol, 2-piperidineethanol, diethanolamine, diglycolamine and diisopropanolamine; and tertiary amines such as N-methyldiethanolamine, N-piperidinemethanol, N-piperidineethanol, N,N-dimethylaminoethanol and 3-quinuclidinol; imidazole and N-functionalised imidazole and amino acids such as taurine, sarcosine and alanine.

The process is particularly effective in capture of CO₂ in the presence of a further amine component selected from tertiary amines and sterically hindered primary and secondary amines.

We have found through pilot plant testing that (aminomethyl)heteroaromatics, particularly the (aminomethyl)pyridines, degrade slowly when the gas stream contains a significant oxygen component which is often the case in combustion gas streams. The resulting product of oxidation is an imine which is a dimer. The formation of the dimer is understood to occur according to the scheme shown below:

The mode of degradation is considered to be unique to aminomethyl substituted aromatics and aminomethyl substituted heteroaromatics as the same dimer stability arising through conjugation with the aromatic ring is not possible for alkyl ckains. The above scheme and stabilisation of the imine is consistent with a synthetic scheme reported for the preparation of more complex heterocyclics such as aromatic and heteroaromatic substituted benzimidazoles in Green Chem., 2013 15, 2713-2717. The resulting imine is favoured as it forms a stable conjugated pi-bonding arrangement. This stabilisation does not extend to aminoalkylsubstituted heteroaromatics in which the alkyl linking group is ethyl or longer chain alkyl which undergo degradation via similar pathways to aliphatic amines such as the formation of carboxylic adds, aldehydes and amino acids (C Gouedard, D Picq, F Launay, P-L Carrette; Int. J. Greenh. Gas Con., 10,244 (2012)).

We have found that formation of the imine and resulting degradation of the aminomethyl-substituted heteroaromatic is inhibited in the presence of an amine, particularly a tertiary amine or sterically hindered primary or secondary amine which has a higher basicity than the aminomethyl-substituted heteroaromatic. For example a pKa at least 0.25 higher than the pKa of the aminomethyiheteroaromatic. In the case of (aminomethyl)pyridines the pK_(a) of 2-(aminomethyl)pyridine, 3-(aminomethyl)pyridine and 4-(aminomethyl)pyridine at 25° C. is 8.6. It is preferred that the further amine particularly a sterically hindered amine or tertiary amine have a pKa of at least 8.85 such as a pKa of at least 9, a pKa of 8.85 to 11.5 or pKa of 9 to 11.5. It is considered that the higher basisity adsorbs protons from the acid gas in solution thereby inhibiting the initial step in the degradation process. In practice the combined use of an (aminomethyl)pyridine with an amine selected from the group consisting of tertiary amines and sterically hindered primary and secondary amines and mixtures thereof of higher basicity, such as 2-amino-2-methyl-1-propanol bas been found to very dramatically reduce the imine formation and resultant degradation of the (aminomethyl)pyridine.

As used herein the term “sterically hindered amine” is defined as those compounds containing at least one primary or secondary amino group attached to either a secondary or tertiary carbon atom. In one embodiment the sterically hindered amine is a secondary amino group attached to either a secondary or tertiary carbon atom or a primary amino group attached to a tertiary carbon atom. Examples of suitable sterically hindered amines and tertiary amines include those shown in the following table with the corresponding pKa at 25° C.

Base pK_(a) at 25° C. 2-amino-1-propanol 9.5 2-amino-2-methyl-1-propanol 9.7 piperidine 11.1 2-piperidinylmethanol 10.1 3-piperidinylmethanol 10.4 4-piperidinylmethanol 10.6 2-piperidinylethanol 10.5 4-piperidinylethanol 10.6 2-(dimethylamino)ethanol 9.2

Other suitable tertiary amines and sterically hindered amines of the required basicity will be readily apparent to those skilled in the art having regard to the above reference degradation mechanism and method of inhibition of imine formation.

Accordingly in a preferred aspect the further amine optionally present in the composition is present in an amount of 10 wt % to 70 wt % the absorbent. In a further aspect the absorbent comprises:

10 wt % to 80 wt % of (aminomethyl)pyridine comprising one or more of 2-(aminomethyl)pyridine, 3-(aminomethyl)pyridine and 4-(aminomethyl)pyridine;

10 wt % to 70 wt % of amine selected from tertiary amines and sterically hindered primary and secondary amines and mixtures thereof of pKa at least 8.85, preferably from 2-amino-1-propanol, 2-amino-2-methyl-1-propanol, piperidine, 2-piperidinylmethanol, 3-piperidinylmethanol, 4-piperidinylmethanol, 2-piperidinylethanol, 4-piperidinylethanol and 2-(dimethylamino)ethanol, and most preferably 2-amino-2-methyl-1-propanol; and

20 wt % to 80 wt % water.

In a further embodiment the absorbent comprises:

20 wt % to 60 wt % of (aminomethyl)pyridine comprising one or more of 2-(aminomethyl)pyridine, 3-(aminomethyl)pyridine and 4-(aminomethyl)pyridine;

10 wt % to 50 wt % of amine selected from tertiary amines and sterically hindered primary and secondary amines and mixtures thereof of pKa at least 8.85, preferably from 2-amino-1-propanol, 2-amino-2-methyl-1-propanol, piperidine, 2-piperidinylmethanol, 3-piperidinylmethanol, 4-piperidinylmethanol, 2-piperidinylethanol, 4-piperidinylethanol and 2-(dimethylamino)ethanol, and most preferably 2-amino-2-methyl-1-propanol; and

20 wt % to 70 wt % water.

The tertiary and sterically hindered amines are typically soluble in the composition at the desired concentration at 25° C. Preferably the tertiary and sterically hindered amines are water soluble at 25° C.

In a further embodiment, the solution comprises an amine absorbent selected from imidazole and more preferably an N-functionalised imidazole. Suitable N-functionalised imidazoles may be found in U.S. Pat. No. 8,741,246, which is incorporated herein by reference.

The suitable N-functionalised imidazoles disclosed in U.S. Pat. No. 8,741,246 are of formula (2):

wherein

R¹ is substituted or unsubstituted C₁₋₂₀ alkyl, substituted or unsubstituted C₂₋₂₀ alkenyl, substituted or unsubstituted C₂₋₂₀ alkynyl, substituted or unsubstituted C₁₋₂₀ heteroalkyl, substituted or unsubstituted C₂₋₂₀ heteroalkenyl, substituted or unsubstituted C₂₋₂₀ heteroalkynyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted thio, substituted or unsubstituted amino, substituted or unsubstituted alkoxyl, substituted or unsubstituted aryloxyl, silyl, siloxyl, cyano, or nitro; and

R², R³, and R⁴ are each independently selected from hydrogen, halogen, hydroxyl, substituted or unsubstituted C₁₋₂₀ alkyl, substituted or unsubstituted C₂₋₂₀ alkenyl, substituted or unsubstituted C₂₋₂₀ alkynyl, substituted or unsubstituted C₁₋₂₀ heteroalkyl, substituted or unsubstituted C₂₋₂₀ heteroalkenyl, substituted or unsubstituted C₂₋₂₀ heteroalkynyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted thio, substituted or unsubstituted alkoxyl, aryloxyl, substituted or unsubstituted amino, cyano, or nitro.

Specific examples of such compounds include the 1-N—(C₁ to C₂₀ alkyl) imidazoles such as 1-butyl imidazole.

In some, embodiment the solution comprises a combination of N-functionalised imidazoles and one or more amines in addition to the substituted heteroaromatic compound.

The one or more amines which may be used in addition to the N-functionalised imidazoles may be selected from the group consisting of primary, secondary and tertiary amines including the specific examples of such amines referred to above.

In another aspect of the invention there is provided a process for removing carbon dioxide gas from a gas mixture including: contacting a gas mixture that is rich in carbon dioxide with an absorbent solution, as described above, to form a target gas rich solution and a gas mixture that is lean in target gas; and desorbing the carbon dioxide gas from the solution. In yet a further set of embodiments there is further provided use of a substituted heteroaromatic compound in aqueous solution at a concentration of at least 20% by weight, based on the total weight of the solution, for absorbing carbon dioxide from a gas stream. Desorbing the carbon dioxide may be facilitated by an increase in temperature, reduction in pressure, change in pH or combination of these factors. It is a significant advantage of the invention that the cyclic capacity of COs brought about by these changes is generally speaking higher for the substituted heteroaromatic compound used in the process of the invention than the molar equivalent of other absorbents such as monoethanolamine.

In one set of embodiments there is further provided a composition comprising an aqueous solution for carbon dioxide gas comprising:

-   -   A. an aqueous solvent;     -   B. at least one absorbent compound comprising the substituted         heteroaromatic compound; and     -   C. an absorbed carbon dioxide, at a concentration above the         equilibrium concentration when the solution is exposed to air at         below the boiling point of the solvent.

Preferably, the concentration of the absorbed carbon dioxide is at least two times (and even more preferably at least five times) the equilibrium concentration when the solution is exposed to air at below the boiling point of the aqueous solvent, thus representing the absorbed carbon dioxide concentration in the solvent during the absorption process as previously described. The background amount of CO₂, will generally be less than 0.1% by weight based on the total weight of the solution. In one embodiment the absorbed carbon dioxide will constitute at least 0.2% by weight based on the total weight of the solution on absorption of the gas more preferably at least 1% and still more preferably at least 10% absorbed carbon dioxide by weight based on the total weight of the solution.

In one embodiment the solution comprises one or more amines in addition to the substituted heteroaromatic compound which additional amines may, for example, be selected from primary, secondary and tertiary amines optionally including N-functionalised imidazoles such as those of formula (2).

In a set of embodiments the total of the absorbent component and water constitute at least 40%, preferably at least 50%, more preferably at least 60%, still more preferably at least 70% and even more preferably at least 80% (such as at least 90%) by weight of the total composition.

FIG. 1 provides an illustration of an embodiment of a process for capture of carbon dioxide from a flue gas stream. The process (100) includes an absorption reactor (102), for absorbing CO₂ from a flue gas stream, and a desorption reactor (104) for desorbing CO₂.

The absorption reactor (102) includes a first inlet (106), a second inlet (108), a first outlet (110), and a second outlet (112), and a gas absorption contact region (114). The first inlet (106) of the absorption reactor (102) is a flue gas inlet through which a CO₂ rich flue gas enters the absorption column (102). The second inlet (108) is an absorbent solution inlet for the aqueous absorbent (such as the substituted heteroaromatic absorbent solutions hereinbefore described) through which a CO₂ lean absorbent enters the absorption column (102). The CO₂ rich flue gas and the CO₂ lean absorbent contact in the gas absorption contact region (114). In this region the CO₂ in the CO₂ rich flue gas is absorbed into the absorbent solution where it is bound in solution to form a CO₂ lean flue gas and a CO₂ rich absorbent solution.

In conducting the process of the invention the aqueous composition may comprise a mixture of optionally substituted heteroaromatic compounds.

The local environment of the solution may be altered in the absorption column to favour the absorption reaction, e.g. to increase absorption of CO₂ into solution where it is bound to the substituted heteroaromatic compound. Such alterations of the local environment may include a change in pH, a change in solution temperature, a change in pressure etc. Alternatively, or additionally, the solution may include other compounds which assist in the absorption of CO₂. These compounds may alter the affinity or absorption capacity of the substituted heteroaromatic compound for CO₂, or these compounds may also absorb CO₂.

If additional compounds are added to the absorbent solution in the absorption reactor (102), the process may additionally include means to remove these compounds.

The absorption of CO₂ from the CO₂ rich flue gas into the absorbent solution results in a CO₂ lean gas and a CO₂ rich absorbent solution. The CO; lean gas may still include some CO₂, but at a lower concentration than the CO₂ rich flue gas, for example a residual concentration of CO₂.

The CO₂ lean gas leaves the absorption column (102) through the first outlet (110), which is a CO₂ lean gas outlet. The CO₂ rich absorbent solution leaves the absorption column through the second outlet (112), which is a CO₂ rich absorbent outlet.

The aqueous composition may, if desired, include solvents in addition to water in order to modify solubility of the substituted aromatic compound and/or other absorbents which may be present composition. Examples of cosolvents may, for example, be selected from the group consisting of glycols, glycol derivatives selected from the group consisting of glycol ethers, glycol ether esters, glycol esters, long chain short chain aliphatic alcohols such as C₁ to C₄ alkanols, long chain aliphatic alcohols, long chain aromatic alcohols, amides, esters, ketones, phosphates, organic carbonates and organo sulfur compounds.

Desorption reactor (104) includes an inlet (118), a first outlet (120), a second outlet (122), and a gas desorption region (124). The CO₂ rich absorbent outlet (112) of the absorption column (102) forms the inlet (118) of the desorption column (104). Desorption of CO₂ from the CO₂ rich solution occurs in the gas desorption region (124).

Desorption of CO₂ from the CO₂ rich solution may involve the application of heat or a reduction in pressure to favour the desorption process. Furthermore, additional compounds may be added to the CO₂ rich solution to enhance the desorption process. Such compounds may alter the solution environment, for example by changing solution pH or altering another parameter to favour the desorption reaction.

Removal of CO₂ from the CO₂ rich solution results in the formation of a CO₂ lean gas stream and a CO₂ lean absorbent solution. The CO₂ lean absorbent solution may still include some CO₂, but at a lower concentration than the CO₂ rich solution, for example a residual concentration of CO₂.

The CO₂ gas stream is taken off via the first outlet (120), which is a CO₂ outlet. The CO lean absorbent solution is taken off via the second outlet (122), which is a CO₂ lean absorbent solution outlet. The CO₂ lean absorbent is then recycled and fed through the second inlet (108) to the absorption column (102).

The invention may be used to absorb carbon dioxide from gas streams having a wide range of carbon dioxide concentration such as from 1 volume % to 99 volume % carbon dioxide. The invention is of particularly practical use in the absorption of carbon dioxide from gas streams, such as flue gas stream, resulting from combustion for fossil fuels such as coal, oil and gas. Typically the carbon dioxide content of such gas streams is in the range of from 3 volume % to 30 volume %. The invention is particularly suited to the capture of carbon dioxide from combustion of fossil fuels and having a carbon dioxide content in the range of from 8 volume % to 20 volume %. Levels of carbon dioxide in the range from 8 volume % to 20 volume % are typically present in the flue gas stream from combustion of fuel gas, fuel oil and coal.

The invention may also be used in capture of other acid gases together with carbon dioxide, such as sulfur dioxide, which may be present in gas streams from combustion of fossil fuels from specific geological sources. The process of the invention provides removal of a substantial amount of CO₂ from the gas stream. For example, in some embodiments, greater than or equal to 50% by volume (vol %); specifically greater than or equal to 70 vol %. Following removal of carbon dioxide from the gas stream in accordance with the invention the lean carbon dioxide gas stream from fossil fuel combustion typically contains no more than about 2 volume % carbon dioxide and more preferably no more than 1.5 volume % carbon dioxide.

The invention will now be described with reference to the following Examples. It is to be understood that the examples are provided by way of illustration of the invention and that they are in no way limiting to the scope of the invention.

EXAMPLES

The chemical abbreviations used in the specification have the following meaning:

-   AMPy: (aminomethyl)pyridine -   2-AMPy: 2-(aminomethyl)pyridine -   3-AMPy: 3-(aminomethyl)pyridine -   4-AMPy: 4-(aminomethyl)pyridine -   MEA: monoethanolamine -   AMP: 2-amino-2-methyl-1-propamol -   BZA: benzylamine -   DMEA: dimethylethanolamine

Example 1

2-AMPy, 3-AMPy, and 4-AMPy were evaluated for CO₂ mass transfer rates together with blends of the amines with monoethanolamine (MEA), 2-amino-2-methyl-1-propanol (AMP), and N,N-dimethylethanolamine (DMEA).

AMPy's have larger CO₂ absorption rates than MEA at low CO₂ loadings. Above 0.3 CO₂ loading, CO₂ absorption rates fall below MEA. AMPy's absorption rates are faster than sterically hindered and tertiary amine absorbents. Equimolar blending with MEA results in faster CO₂ absorption rates at low CO₂ loadings at a similar overall concentration to MEA while maintaining a similar absorption rate to MEA at high CO₂ loadings above 0.3.

AMPy's and their blends were evaluated here for their CO₂ absorption rates using a wetted-wall column contactor.

Experimental Method

A general schematic of the Wetted Wall Column (WWC) apparatus is shown in FIG. 2a and an expanded view of the column portion of the WWC is shown in FIG. 2b . The WWC apparatus (1) is comprised of a first portion (10) comprising a hollow stainless steel column (11) extending from a base (12) having an inlet (13) for gas stream containing carbon dioxide and received in a second housing portion (20) comprising a temperature controlled jacket (21) and a gas outlet (22). The column (11) has an effective height and diameter of 8.21 cm and 1.27 cm respectively. About 0.65 L of amine solution within in a submerged reservoir held in a temperature controlled water bath is pumped up the inside (14) of the column (11) before exiting through small outlet holes (15) in the top (16) of the column (11). The exiting liquid falls under gravity over the outside (17) of the column (11) forming a thin liquid film before collecting at the base (12) of the column portion (10). The solution is returned from an outlet (19) on the base (12) to a reservoir in a closed loop configuration. Thus, the liquid flowing over the outside (16) of column (12) is constantly replenished with fresh amine solution from the reservoir. The temperature of the column (20) and surrounding gas space (23) is controlled by a glass jacket (21) connected to the water bath.

The total liquid flow rate within the apparatus was maintained at 121.4 mL·min⁻¹ (2.02 mL·s⁻¹) as indicated by a calibrated liquid flow meter. A mixed CO₂/N₂ gas was prepared by variation of Bronkhorst mass flow controllers for CO₂ and N₂ respectively to achieve a total gas flow rate of 5.0 L min⁻¹. Prior to entering the column (12) the gas stream is passed through a ⅛″ steel coil and saturator located in a water bath. Liquid and gas flow rates were selected to achieve a constant smooth and ripple free liquid film on the outside of the column (12). The absorption flux into the amine solutions, N_(CO2), was measured as a function of dissolved CO₂ loadings from 0.0-0.4 moles CO₂/total mole amine and over a range of CO₂ partial pressures spanning 1.0-20.0 kPa. The composition of the gas stream prior to and exiting the housing (20) was monitored via a Horiba VA-3000 IR gas analyser. CO₂ loaded amine solutions were prepared by bubbling a pure CO₂ gas stream into a known volume of amine solution and the resulting mass change in the solution used to indicate CO₂ loading. A tower of condensers was connected to the outlet of the flask to ensure loss of amine and water vapour was minimised.

The amount of CO₂ absorbing into the amine liquid was determined from the CO₂ content of the gas stream entering (bottom) and exiting (top) the housing (20). The former was measured while bypassing the absorption column with the gas stream passing directly to the gas analyser. The absorption flux, expressed in millimoles (mmoles) of CO₂ absorbed per second per unit area of contact between liquid amine and gas, was determined over a range of CO₂ partial pressures in each of the amine solutions and CO₂ loadings.

CO₂ mass transfer co-efficients, K_(G), incorporate the processes of physical absorption and chemical reaction, into a single value. Ideally, absorbents with larger CO₂ mass transfer rates result in smaller absorption equipment and significant cost reductions.

K_(G) values as a function of CO₂ loading are presented in 1, FIG. 3 and FIG. 4. From the curves in the figures CO₂ mass transfer is faster in 4-AMPy solutions at low CO₂ loadings compared to MEA at similar concentrations. The absorption rate declines with increasing CO₂ loading and is 50% lower than MEA towards higher loadings of 0.4. In practice this does not present an issue due to the faster absorption at low CO2 loading which offsets the lower rate at high loading. The larger cyclic capacity also means the AMPy's tend to more easily be stripped to low loadings where the mass transfer is shown in Table 4.

The trend in K_(G) at low CO₂ loadings follows 2-AMP>3-AMPy>4-AMPy. The superior reactivity of 2 and 3-AMPy over 4-AMPY respectively is believed to extend from the increased basicity of the amines. CO₂ mass transfer is similar among the AMPy's at high CO₂ loadings. Equimolar blends of 3.0M 3-AMPY with DMEA and AMP result in lower CO₂ mass transfer rates than 6.0M MEA over the entire CO₂ loading range. A similar blend of 4-AMPy with MEA results in increased CO₂ mass transfer at low CO₂ loadings (˜35% at 0.0 CO₂ loading) and similar CO₂ mass transfer at high loadings.

TABLE 1 Overall CO₂ mass transfer co-efficients, K_(G) for (aminomethyl)pyridines and their blends. Overall CO₂ mass CO₂ loading transfer co-efficient Absorbent composition (moles CO₂/ K_(G) (mmol · m⁻² · (M) total mole amine) ^(s−1) · Pa⁻¹) 4-(aminomethyl)pyridine 3.0M 4-AMPγ 0 1.9 0.2 1.49 0.4 0.677 5.0M 4-AMPγ 0 2.706 0.2 1.545 0.373 0.68 6.0M 4-AMPγ 0 2.86 0.2 1.75 0.4 0.412 3.0M 4-AMPγ + 3.0M MEA 0 3.25 0.2 1.994 0.4 0.83 3.0M 4-AMPγ + 3.0M AMP 0 2.197 0.201 1.392 0.406 0.572 3.0M 4-AMPγ + 3.0M DMEA 0 2.364 0.2 1.444 0.4 0.5799 3-(aminomethyl)pyridine 3.0M 3-AMPγ 0 1.77 0.2 1.462 0.4 0.465 5.0M 3-AMPγ 0 2.74 0.2 1.57 0.4 6.0M 3-AMPγ 0 3.19 0.2 1.77 0.4 0.35 3.0M 3-AMPγ + 3.0M MEA 0 3.56 0.2 2.16 0.4 0.702 3.0M 3-AMPγ + 3.0M AMP 0 2.71 0.2 1.51 0.4 0.514 2-(aminomethyl)pyridine 3.0M 2-AMPγ 0 2.26 0.2 1.55 0.4 0.593 5.0M 2-AMPγ 0 2.88 0.2 1.82 0.4 0.459 6.0M 2-AMPγ 0 3.57 0.2 1.85 0.4 0.326

Importantly, blending with DMEA and AMP results in similar viscosities to standalone AMPy absorbents at similar concentrations and low (or zero) CO₂ loading. Viscosity of the 4-AMPy/AMP blend increases with CO₂ loading similarly to the standalone 6.0M 4-AMPy absorbent while the viscosity of the blend with DMEA increases at a slower rate (˜40% lower viscosity at 0.4 loading). Viscosity of the 4-AMPy/MEA blend is substantially lower at all CO₂ loadings (˜75% lower viscosity at 0.4 CO₂ loading). A number of the AMPy/MEA blends exhibited similar or larger CO₂ mass transfer rates than the standalone absorbents indicating that blended absorbents are useful.

The larger physical CO₂ solubility in the AMPy's makes up for the lower reaction kinetics.

TABLE 2 Protonation constants from 15.0-45.0° C. together with corresponding enthalpies and entropies for 2-(aminomethyl)pyridine, 3-(aminomethyl)pyridine, and 4-(aminomethyl)pyridine respectively. BZA data included for comparison. Temperature (° C.) ΔH° ΔS° 15 25 35 45 kJ · mol⁻¹ J · mol⁻¹ · K⁻¹ 1/T (K) 0.00347 0.00335 0.00324 0.00314 4-AMPy log K prot 8.77 8.43 8.08 7.86 −53.9 19.6 log K carb Prot 2 3.84 3.65 3.48 3.41 −25.5 15.3 3-AMPy log K prot 9.11 8.83 8.51 8.26 −50.6 0.8 log K carb Prot 2 3.42 3.34 3.25 3.17 −14.5 −15.2 2-AMPY log K prot 8.98 8.68 8.41 8.19 −46.6 −10.1 log K carb Prot 2 1.96 1.86 1.75 −17.9 24.5 BZA* log K prot 9.77 9.43 8.95 8.61 −59.5 20 *Single protonation only

The table shows the larger enthalpy of reaction for the AMPy's which leads to more CO₂ release with increasing temperature. This contributes to the good cyclic capacity of the substituted heteroaromatic compounds.

From the data in Table 2 the first protonation constants of AMPy, log K prot are similar to MEA and BZA and fall within a suitable range for CO₂ capture processes. Importantly, the large and desired protonation enthalpy (ΔH⁰) observed for BZA is largely maintained in the AMPy derivatives (−53.9 to −46.6). This large enthalpy is a unique feature and is responsible for the superior cyclic capacity compared to other non-aromatic and cyclic amine absorbents.

TABLE 3 4-AMPy carbamate stability constants from 15.0-45.0° C. together with corresponding enthalpies and entropies for 4 and 3-(aminomethyl)pyridine. Temperature (° C.) ΔH° ΔS° 15 25 35 45 kJ · mol⁻¹ J · mol⁻¹ · K⁻¹ 1/T (K) 0.00347 0.00335 0.00324 0.00314 4-AMPy log K carb 2.35 2.22 2.02 1.84 −30.05 −58.97 log K carb Prot 7.15 6.95 6.69 6.52 −38.08 4.91 3-AMPy log K carb 2.34 2.11 1.93 1.70 −36.83 82.97 BZA log K carb 2.20 2.01 1.81 1.58 −36 −82 MEA log K carb 1.85 1.76 1.66 1.55 −18 −35

TABLE 4 CO₂ loadings and cyclic capacities for 6.0M solutions of 4-AMPy, MEA, and BZA respectively together with data for an equimolar blend containing 3.0M 4-AMPy and 3.0M MEA. CO₂ loading @ 15 kPa CO₂ cyclic Temperature (° C.) 40 120 capacity 6.0M 4-AMPy 0.50 0.10 0.40 6.0M MEA 0.52 0.32 0.20 6.0M BZA 0.50 0.13 0.37 3.0M 4-AMPy + 3.0M MEA 0.50 0.23 0.27

The larger cyclic capacity of the (aminomethyl)pyridines produces lower operating energy requirements of the process. As a result less absorbent is required to capture the same amount of CO₂ thereby lowering circulation rates and reboiler duties.

Example 2: Benzylamine Comparison

Benzylamine (BZA) has been found to form solid precipitate salts in the presence of CO₂, particularly at high concentrations of BZA in the liquid phase, limiting the optimum operating concentration to <30 wt % (˜2.8 M). It was also found that BZA has the propensity to form small amounts of solid precipitates in the gas phase due to non-ideal liquid behaviour leading to elevated vapour pressures above those predicted by Raoult's law at low CO₂ loadings. As part of the absorbent screening process concentrated aqueous 3-AMPy was evaluated for its potential to form solid precipitates in the presence of CO₂ at high concentrations. While similar in structure to BZA the incorporation of a second nitrogen group into the aromatic ring was found to increase solubility of the carbamate product in aqueous solution. A simple bubble reactor was utilised to determine the precipitation propensity while passing a pure CO₂ gas stream at atmospheric pressure into a concentrated 3-AMPy solution held at ambient temperature. A concentration of 80 wt % 3-AMPy was achieved before precipitation of the carbamate salt was observed. While a precipitate was observed, it is unlikely this will occur in the pilot plant given the aggressive conditions employed in the simple lab based study. Furthermore, similar precipitation behaviour has been observed for other common aqueous amines in highly concentrated solutions but which are operated successfully in pilot plants.

Example 3: VLE Measurements for AMPy Derivatives and Blends

The capacity of an absorbent solution for CO₂ is a vital requirement for absorbent development. CO₂ capacity drives the optimum absorbent concentration, energy requirements, and liquid equilibrium (VLE) measurements are typically used to determine absorption capacities, cyclic capacities (temperature dependence), and absorption enthalpies (temperature dependence of CO₂ solubility at a given CO₂ loading). Vapour liquid equilibrium also can be predicted from knowledge of the equilibrium constants for CO₂/H₂O chemistry, amine protonation, carbamate stability, and physical CO₂ solubility (Henry's constant). VLE data can also be used to regress equilibrium constants for carbamate stability which can be used to verify those determined from independent NMR studies (rarely available for bespoke absorbents).

The vapour liquid equilibrium apparatus used here incorporates a sealed stainless steel reactor (4 independent vessels) and high pressure CO₂ gas delivery system. Absorbent liquid (5.0 mls) is placed into vessels and evacuated several times to remove any residual CO₂ gas that may be present. The vessels are charged with high pressure nitrogen (˜2.0 BAR absolute pressure) before the mass is recorded using a milligram balance. Once weighed the vessel pressure sensor is attached and the entire vessel placed into an oven at the desired temperature (40, 60, 80° C.). Following overnight equilibration, the initial pressure of the vessel (now incorporating contributions from N₂ and H₂O) is recorded and the vessel charged with CO₂ (˜5.0 BAR absolute pressure). The vessel is weighed and the mass of CO₂ dosed into the vessel recorded. The vessel is returned the oven and equilibrated for 24 hours or until steady state is reached (indicated by no further changes in pressure). Samples from the vessel headspace are then analysed by gas chromatography to determine the gas phase CO₂ partial pressure. The liquid phase CO₂ loading is then determined by mass balance calculation.

The results for 6.0M 3-AMPy are shown in Table 5 below:

22° C. 40° C. 60° C. CO₂ CO₂ CO₂ mol Partial mol Partial mol Partial CO₂/mol Pressure CO₂/mol Pressure CO₂/mol Pressure 3-AMPγ (KPa) 3-AMPγ (KPa) 3-AMPγ (KPa) 0.43 0.53 0.43 2.90 0.43 16.53 0.41 0.34 0.39 1.14 0.38 5.70 0.39 0.21 0.34 0.51 0.35 3.29 0.37 0.12 0.31 0.29 0.27 1.40 0.35 0.097 0.17 0.064 0.21 0.67 0.32 0.082 0.12 0.24 0.28 0.043 0.11 0.19 0.26 0.093 0.022 0.030 0.22 0.017

Example 4: Energy Performance and Mass Transfer

A concentrated 3-AMPy absorbent operating at 6.0M was selected as the base case given its simplicity. Alternative blends incorporating equimolar concentrations of monoethanolamine (MEA) and 2-amino-2-methyl-1-propanol (AMP) with 3-AMPy (i.e. 3.0M 3-AMPY+3.0M MEA or 3.0M AMP respectively) were selected to provide rapid kinetic or improved thermodynamics while minimising the cost of the absorbent inventory for large scale evaluation in a pilot plant.

FIG. 7 of the drawings shows the model estimated reboiler duties as a function of the ratio of liquid and gas flow rates (UG) for an isobaric stripping column with a range of aqueous absorber solutions including 6M 3-AMPy and various ratios of 3-AMPy and AMP (with 30 wt % MEA included for comparison). These represent some of the more practically useful formulations in terms of energy requirement, with formulations incorporating MEA having poorer energy performance. There is little impact from the addition of AMP. AMP was, however, found to have a significant positive effect on mass transfer.

Operation of the aqueous 6M 3-AMPy absorbent was completed over about 1 month in a pilot plant of general operation shown in FIG. 1. A parametric study was undertaken to estimate the CO₂ stripping energy requirement as a function of operating parameters for a traditional absorber-stripper process design. Overall favourable results were found for the energy requirement as shown in the figure below.

Unlike the previously tested formulation based on BZA, no operational issues were encountered with an aqueous solution of 6M 3-AMPy. No precipitation or foaming events occurred nor were there any issues regarding volatility.

As can be seen in FIG. 8 the energy requirement using aqueous solutions of (aminomethyl)pyridines such as 6M 3-AMPy is much lower than for monoethanolamine (MEA).

Example 5: Pilot Plant Trials Using 3-(Aminomethyl)Pyridine (3-AMPy) Based Absorbents

Extended pilot plant trials have been undertaken using a 0.4 tonne/day —CO₂ capture plant located at a brown coal power station. The capture plant was operated with a flue gas slip-stream of flow rate 80 m³/hr directly taken from the power station.

Example 5a: Pilot Plant Trials Using Absorbent Containing 6 Mol/L Aqueous 3-AMPy (61 wt % 3-AMPy and 39 wt % Water)

The campaign with 6 mol/L Aqueous 3-AMPy was operated for a duration of approximately 1500 hours. During operation the performance of the plant was assessed in terms of reboller energy requirement and the degradation of the amine was monitored. The single dominant degradation product formed was also identified and characterised. Minimum reboiler duties of 2.9 and 2.6 GJ/tonne CO₂ without and with use of the rich split process configuration respectively were achieved. This is compared to 3.3 GJ/tonne CO₂ for 5 mol/L monoethanolamine (MEA) in both configurations.

In laboratory testing under accelerated degradation conditions the dominant degradation product formed was found to be an imine dimer of 3-AMPy. Monitoring of loss of amine and formation of the imine was undertaken during the campaign by infrared (IR) spectroscopy and high performance liquid chromatography (HPLC). Additional analysis of plant samples by ¹³C and ¹H-NMR spectroscopy confirmed that the previously identified imine was the primary degradation product in the plant.

FIG. 9 is a plot of the trend in amine and imine concentration during the pilot plant campaign.

During the pilot plant trial the degradation reaction mechanism was investigated in the laboratory by breaking the overall reaction down into the possible individual chemical transformations and testing if they occurred. The determined mechanism proceeds via a protonated 3-AMPy molecule and loss of an ammonium ion followed by oxidation. The complete of degradation mechanism of 3-AMPy to an imine via reaction with oxygen is shown in the following Scheme.

Example 5b: 3 Mol/L 3-AMPy and 3 Mol/L 2-Amino-2-Methyl-1-Proponal (AMP) (32 wt % 3-AMPy, 26 wt % AMP and 42 wt % Water)

Based on the degradation mechanism of the above scheme it was considered that if 3-AMPy was formulated with a stronger base to reduce the formation of protonated 3-AMPy during CO₂ absorption, its degradation could be suppressed. AMP was chosen as the amine for formulation as it has the required basicity and is known to be robust in CO₂ capture applications. AMP does not react directly with CO₂ but rather acts as a base to preferentially accept the protons released when 3-AMPy reacts. Simulations indicated that the concentrations used in the absorbent of aqueous 3 mol/L 3-AMPy and 3 mol/L 2-amino-2-methyl-1-proponal (AMP) were optimal to reduce degradation and maintain capture performance.

A pilot plant campaign was conducted with the aqueous absorbent of Example 5b for 5000 hours. It was possible to conduct a much longer campaign as the degradation of the absorbent was much slower than the absorbent of Example 5a. The same reboiler energy requirements were achieved as in Example 5a. FIG. 10 shows the concentrations of 3-AMPy, AMP and imine over the duration of the campaign. The rate of imine formation was orders of magnitude lower than seen in the trial of Example 5a. In addition the overall rate of degradation of was found to be 10 times slower than 5 mol/L MEA.

The formation of the imine dimer and inhibition of degradation is a unique property of aminomethylaromatic systems and in particular enhances the performance on aminomethyl substituted heteroaromatics. Aminoalkylpyridine with longer bridging chains such as ethyl and propyl between the amino and pyridine group do not form the imine and degrade via chain loss and more traditional mechanism that form products that cannot be easily regenerated.

FIG. 10 3-AMPy, AMP and imine concentrations measured during the pilot plant campaign by IR spectroscopy over 5000 hours of operation.

In contrast with the reduction in the concentration of 3-AMPy shown in FIG. 9 the composition of Example 5b consisting of aqueous 3 mol/L 3-AMPy and 3 mol/L 2-amino-2-methyl-1-proponal (AMP) (32 wt % 3-AMPy, 26 wt % AMP and 42 wt % water) showed little reduction in the concentration of the amines over the period of 5000 hours operation of the pilot plant under the same conditions.

Example 6: Comparison of the Absorbent of Example 5 with MEA

The pilot plant was also operated with 5 mol/L (30 wt %) aqueous monoethanolamine (MEA) for approximately 500 hours. This allowed optimum reboiler duties to be identified for each absorbent via parametric study. These optimum reboiler duties and rates of amine degradation are shown in Table 6 below and are for the standard plant configuration (no rich split). Note that the MEA degradation information is taken from literature as it was only run for a short duration in the pilot plant.

TABLE 6 5 mol/L MEA Example 5a Example 5b Reboiler duty 3.4 2.9 2.9 (GJ/tonne CO₂) Amine degradation 1.5* 23 0.16 rate (kg/tonne CO₂) *Degradation rate taken from book P. Feron, Absorption-Based Post-Combustion Capture of Carbon Dioxide, Elsevier (2016).

Example 7: Anilne/Aminopyridines

Aniline and aminopyridine compounds lack the basicity required to effectively act as CO₂ absorbents. The pKa of their conjugate acids is smaller than or similar to that of CO₂ in aqueous solution (6.3 at 25° C., T J Edwards, G Maurer, J Newman, J M Prausnitz; AIChE J., 24,966 (1978)). The pKa of the conjugate bases is shown in Table 7 below. Thus they are unable to accept protons from CO₂ ionisation. In addition they will only directly react with CO₂ to form a carbamate in the presence of a strong base (P V Kortunov, L S Baugh, M Siskin, D C Calabro; Energy & Fuels, 29,5967 (2017)). This lower basicisity compared to aliphatic amines is due to the delocalisation of the lone pair of electrons on the nitrogen into the aromatic ring. 4-Aminopyridine is a special case due to the larger pK_(a) of its conjugate acid, which is in a suitable range for CO₂ absorption. This is due to resonance structure stabilisation of the ion, but this stabilisation renders it unable to react directly with CO₂ to form a carbamate (A Albert, R Goldacre, J Phillips; J. Chem. Soc., 455,2240 (1948)).

TABLE 7 pK_(a) of conjugate acid at Compound 25° C. in water Aniline 4.6 2-Aminopyridine 6.7 3-Aminopyridine 6.3 4-Aminopyridine 9.5 2-(Aminomethyl)pyridine 8.7 3-(Aminomethyl)pyridine 8.8 4-(Aminomethyl)pyridine 8.4

Example 8: Stability of aminoalkylaromatics

Relationship between structural rigidity and CO₂ capture performance.

The enthalpy of protonation is an important parameter in aqueous amine absorbents. The larger the enthalpy of protonation the larger the CO₂ cyclic capacity that can be achieved via a temperature swing process. A relationship exists between the enthalpy and entropy of protonation and it is described in the publication D Fernandes, W Conway, X Wang, R Burns, G Lawrance, M Maeder, G Puxty; J. Chem. Thermodynamics, 51,97 (2012). In summary, the more structurally rigid a molecule, the more negative the enthalpy of protonation and smaller and/or more negative the entropy of protonation. This effect is due to reduced internal degrees of freedom resulting in smaller entropy changes upon protonation. Thus aminomethyl substituted heteroaromatic groups have more favourable enthalpy of protonation properties than longer alky chain bridging groups such as ethyl or propyl bridging groups or aliphatic amines. FIG. 11 compares the enthalpy and entropy of protonation of a range of amines. The red squares are allow comparison of 4 different aminomethyl aromatic compounds to 2-phenyethylamine to illustrate this relationship.

Example 9: Bases to Prevent Degradation of (Aminomethyl)Pyridines

As shown in Example 5b the presence of AMP in the absorber composition inhibited the formation of the imine produced by dimerization of the AMPy derivative formed on absorption of CO₂. Other bases including amines of higher pKa than the (aminomethyl)pyridine may also be used in this role. Preferred bases are tertiary and sterically hindered amines which are stable and provide a proton accepting role on CO₂ absorption. The average pKa of 2-(aminomethyl)pyridine, 3-(aminomethyl)pyridine and 4-(aminomethyl)pyridine at 25° C. is 8.6

Suitable bases typically have a pKa at least 0.25 units higher than the pKa of the (aminomethyl)pyridines, that is about 0.25 units higher than 8.6 (this represents a 2.5× increased selectivity for protons). Examples of suitable tertiary and sterically hindered amines include those specified in Table 8 together with the pKa at 25° C.

TABLE 8 Base pK_(a) at 25° C. 2-amino-1-propanol 9.5 2-amino-2-methyl-1-propanol 9.7 piperidine 11.1 2-piperidinylmethanol 10.1 3-pipendinylmethanol 10.4 4-pipendinylmethanol 10.6 2-piperidinylethanol 10.5 4-piperidinyiethanol 10.6 2-(dimethylamino)ethanol 9.2 

The invention claimed is:
 1. A process for absorbing carbon dioxide from a gas stream containing carbon dioxide, comprising contacting the gas stream with an absorbent comprising an aqueous composition comprising at least 10 wt % water and a substituted heteroaromatic compound according to formula Ia:

wherein R¹ is methylene; R⁴ is an optional carbon substituent selected from the group consisting of C₁ to C₄ alkyl, hydroxy, hydroxy-C₁ to C₄ alkyl, C₁ to C₄ alkoxy, C₁ to C₄ alkoxy-(C₁ to C₄ alkyl); and n is 0, 1 or
 2. 2. The process of claim 1, wherein the substituted heteroaromatic compound is selected from the group consisting of: 2-(aminomethyl)pyridine, 3-(aminomethyl)pyridine and 4-(aminomethyl)pyridine.
 3. The process of claim 1, wherein the substituted heteroaromatic compound is 3-(aminomethyl)pyridine.
 4. The process of claim 1, wherein the concentration of substituted heteroaromatic compound is 1 wt % to 80 wt % of the aqueous composition.
 5. The process of claim 1, wherein the substituted heteroaromatic compound is dissolved in the aqueous solution in an amount of at least 20 wt % of the water content of the aqueous composition.
 6. The process of claim 1, wherein the concentration of the substituted heteroaromatic compound is 10 wt % to 80 wt % of the aqueous composition.
 7. The process of claim 1, wherein the aqueous composition comprises an additional amine selected from tertiary amines, sterically hindered amine and mixture thereof having a pKa greater than that of the substituted heteroaromatic compound.
 8. The process of claim 1, wherein the aqueous composition further comprises a tertiary amine, sterically hindered amine or mixture thereof having a pKa at least 8.85 at 25° C.
 9. The process of claim 1, wherein the aqueous composition further comprises a carbon dioxide absorbent which is selected from the group consisting of Imidazole and N-functionalised imidazole.
 10. The process of claim 1, wherein the aqueous composition comprises the substituted heteroaromatic compound in an amount of 10 wt % to 80 wt % of the aqueous composition and further absorbent wherein the weight ratio of the substituted heteroaromatic compound to further absorbent is from 1:10 to 10:1.
 11. The process of claim 1, wherein the water content of the aqueous composition is at least 15 wt %.
 12. The process of claim 1, wherein the absorbent comprises 10 wt % to 60 wt % of (aminomethyl)pyridine comprising one or more of 2-(aminomethyl)pyridine, 3-(aminomethyl)pyridine and 4-(aminomethyl)pyridine; 10 wt % to 60 wt % of amine selected from tertiary amines and sterically hindered primary and secondary amines and mixtures thereof of pKa at least 8.85; and 20 wt % to 80 wt % water.
 13. The process of claim 12 wherein the amine selected from tertiary amines and sterically hindered primary and secondary amines is selected from the group consisting of 2-amino-1-propanol, 2-amino-2-methyl-1-propanol, piperidine, 2-piperidinylmethanol, 3-piperidinylmethanol, 4-piperidinylmethanol, 2-piperidinylethanol, 4-piperidinylethanol, 2-(dimethylamino)ethanol and mixtures of two or more thereof.
 14. A composition of absorbed carbon dioxide comprising: A. an aqueous solvent containing water in an amount of at least 10 wt % of the composition; B. at least one absorbent compound for carbon dioxide comprising a substituted heteroaromatic compound according to formula Ia

wherein R¹ is methylene, R⁴ is an optional carbon substituent selected from the group consisting of C₁ to C₄ alkyl, hydroxy, hydroxy-C₁ to C₄ alkyl, C₁ to C₄ alkoxy, C₁ to C₄ alkoxy-(C₁ to C₄ alkyl); and n is 0, 1 or 2; and C. absorbed carbon dioxide, wherein the absorbed carbon dioxide is at a concentration above the equilibrium concentration when the solution is exposed to air at below the boiling point of the solvent.
 15. The composition of claim 14, wherein the absorbed carbon dioxide constitutes at least 1% absorbed carbon dioxide by weight based on the total weight of the composition.
 16. The composition of claim 14, wherein the substituted heteroaromatic compound is selected from the group consisting of: 2-(aminomethyl)pyridine; 3-(aminomethyl)pyridine; or 4-(aminomethyl)pyridine.
 17. A composition claim 14, wherein, the solution comprises an additional amine selected from the group consisting of tertiary amines, sterically hindered amines and mixtures thereof having a pKa greater than that of the substituted heteroaromatic compound.
 18. The composition of claim 14, wherein the concentration of substituted heteroaromatic compound is 1 wt % to 80 wt % of the aqueous composition.
 19. The composition of claim 14, wherein the absorbent composition comprises 10 wt % to 60 wt % of (aminomethyl)pyridine comprising one or more of 2-(aminomethyl)pyridine, 3-(aminomethyl)pyridine and 4-(aminomethyl)pyridine; 10 wt % to 60 wt % of amine selected from tertiary amines and sterically hindered primary and secondary amines and mixtures thereof of pKa at least 8.85; and 20 wt % to 80 wt % water.
 20. The process of claim 1, wherein the absorbent does not include an ionic liquid. 